Phenyl carboxamido monoazo dyes



United States Patent 3,262,924 PHENYL CARBOXAMIDO MONUAZO DYES MiltonGreen, Newton Center, Mass., assignor to Polaroid Corporation,Cambridge, Mass, a corporation of Delaware No Drawing. Filed Feb. 15,1962, Ser. No. 173,349

a 7 Claims. (Cl. 260-163) This application is a continuation-in-part ofapplication Serial No. 703,515 filed December 18, 1957, and nowabandoned.

This invention relates to chemistry and, more particularly, to novelchemical compounds which are useful in preparing monochromatic andmultichromatic photographic images.

U.S. Patent No. 2,983,606, issued on May 9, 1961, to Howard G. Rogers,discloses diffusion transfer processes wherein a photographic negativematerial such as a photographic element comprising an exposed silverhalide emulsion layer containing a latent image, is processed using acompound which is both a dye and a silver halide developer anddesignated as a dye developer, thereby imparting to the image-receivingelement a reversed or positive dye image. In carrying out the process ofthis patent, a photosensitive element containing a silver halideemulsion is exposed and permeated with a liquid processing composition,for example, by immersing, coating, spraying, flowing, etc., in thedark, and the thus permeated exposed photosensitive element is broughtinto superposed relationship with an image-receiving layer. In apreferred embodiment, the photosensitive element contains a layer of dyedeveloper and the liquid processing composition permeating thephotosensitive element provides a solution of dye developersubstantially uniformly distributed therein. As the exposed silverhalide emulsion is developed, the oxidation product of the dye developeris immobilized or precipitated, in situ, with the developed silver,thereby providing an imagewise distribution of unoxidized dye developerdissolved in the liquid processing composition. At least part of theimagewise distribution of unoxidized dye developer is transferred, byimbibition, to the superposed image-receiving layer or element to formthe dye transfer image. While the dye developer may be utilized in thephotosensitive element, for example, in, on, or behind the silver halideemulsion, it may also be utilized in the image-receiving element or inthe liquid processing composition.

The present invention relates to novel dye developers which areparticularly useful in photographic processes, products andcompositions, such as described above and disclosed with moreparticularity in the aforementioned US. Patent No. 2,983,606.

One object of this invention, therefore, is to provide novel chemicalcompounds and novel syntheses for preparing these novel compounds.

Another object of the invention is to provide novel chemical compoundsuseful in photographic products, processes and compositions in whichcolor developing agents are used to develop a latent image.

Yet another object of the invention is to provide novel chemicalcompounds useful in preparing monochromatic and multichromaticphotographic images.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the product possessing the features,properties and the relation of comice ponents which are exemplified inthe following detailed disclosure, and the scope of the application ofwhich will be indicated in the claims.

For a further understanding of the nature and objects of the invention,reference should be had to the following detailed descriptioni The novelcompounds of this invention are azo dye developers, that is, azo dyescontaining at least one and not more than two silver halide developingfunctions, or derivatives thereof having a protecteddeveloping function,that is, one or two aromatic groups which upon hydrolysis form adeveloping function. In other words, the novel compounds of thisinvention comprise an azo dye having at least one and not more than twosubstituents of the following formula:

wherein R is hydrogen or an alkyl group, preferably a lower alkyl group,such as for example, methyl, ethyl, etc.; and R and R may be the same ordifferent or may be hydroxyl or acyloxy groups. The term acyloxy as usedherein is meant to signify the grouping i R (JO- wherein R is an aryl,alkyl, aryloxy, or alkoxy group, and the term dye developer as usedherein is intended to signify the compounds of Formula A wherein both Rand R are hydroxyl groups.

It will be apparent that the novel compounds of this invention may alsobe represented by the formula:

wherein R the represents the radical of an azo dye molecule wherein R, Rand R have meanings previously noted;

Y may be -N=NQ, or a pyrazolone dye radical linked to the phenyleneradical of said substituent through the free nitrogen atom of saidpyrazolone nucleus; and Q represents an azo coupler, such as, forexample, a pyrazolone or naphthol azo coupler radical.

As illustrations of azo dyes within the scope of this invention, mentionmay be made of the following compounds:

1 OH O H 4- (4'- [p- 2 ,5 -dlhydroxyphenyl) -phenylcarboxamidophenylazo)-3-methyl-1-phenyl-5-pyrazolone 3) OH 0 H OH l N=N 6 63 6E60H,

2- (4-[p-(2",5"-dlhydroxyphenyl) -pl1enylcarboxamldo phenylazo)-4-meth0xy-1-naph th-ol 2- 4'- [p- 2 ,5 -bls-cuthyloxyphenyl)-phenylcarboxamido phenylazo) -4-methoxy-1-naphtho1 3-curbethoxy-4- 4'-[m- 2",5 -dihydroxyphenyl) -phenylcarboxamldo] -phenylaz0)-1-pheny1-5-pyrazo1one 0 on, NN ('5 N/ F n 0 N C a H N/ on 0 ll HNC 1(4' [m (2",5"-dihydroxyphenyl)-benzamido]-phenyl)- 3 N,Ndimethylcarboxamido 4 (2,4,6-trlmethylphenylaZo)-5-pyraz01one Thecompounds of this invention containing an amino or substituted aminogroup may also be present in the form of acid addition salts such as,for example, the hydrochloride.

One method of preparing the novel compounds of this invention comprisesreacting, in the presence of a suitable halogen acid acceptor such as,for example, quinoline, anhydrous pyridine, etc., a compound of theformula:

( acyloxy i C-halogen acyloxy with an azo dye containing not less thanone and not more than two reactive primary or secondary amino groups,such as for example, 4-(p-aminophenylazo)-3-methyl-l-phenyl-S-pyrazolone; 2 (p-aminophenylazo)-4phenylazo-S-pyrazolone, etc.

Another method of preparing the novel compounds of this inventioncomprises reacting, in the presence of a suitable halogen acid acceptor,a compound of Formula D with a compound of the formula:

( R N ArX wherein R has the same significance as previously noted; Ar isan arylene nucleus, i.e., phenylene; and X is a group convertible to aprimary amino group subsequent to reaction such as, for example, a nitrogroup. The resulting primary amine may be diazotized and coupledaccording to conventional methods to provide suitable compounds withinthe scope of this invention.

After reaction and prior to use as a photographic dye developer, therespective acyloxy groups may be removed by deesterification such as forexample, by hydrolysis in the presence of alkali to form thehydroquinonyl developing function.

However, it is to be noted that where desired the respective acyloxygroups of the aforementioned intermediate products, which may berepresented by the formula:

(F) acyloxy a cyloxy wherein Ar and R have the meanings heretofore givenand X is a nitro or a primary amino group; may also be removed bydeesterification and the resulting dihydroxyphenyl products thereof maythen be utilized as photographic developing agents.

As examples of compounds contemplated within the scope of Formula F andthe free hydroquinonyl forms thereof, mention may be made of:

I OH

4- (p [2,5'-dihydroxyphenyl]-phenylcarboxamido)-an1line 4- (p- [25-bis-cathyloxypl1enyl] -phenylcarboxamido -aniline 9 O H H I O H 4-(19- [2',5'-dihydroxypheny1] -phenylcarb0xamid0)- nitrobenzene4-(p-[2,5-bis-cathyloxypheny1] phenylcarboxamido)- nitrobenzene Theinvention will be illustrated in greater detail in conjunction with thefollowing specific examples which set out representative preparations ofthe novel compounds of this invention, which however are not limited tothe details therein set forth and are intended to be illustrative only.

Example I To a hot solution of 7 g. of p-carboxyphenylquinone, preparedaccording to the procedure of Kvalnes in JACS 56, 2478 (1934), in 350cc. of 95% ethanol is added a solution of 10 g. of sodium hyposulfite in40 cc. of water. The original amber color discharges, and a whiteprecipitate forms which is removed by filtration. The filtrate isacidified with 10 cc. of concentrated hydrochloric acid and a Whiteprecipitate forms which is removed by filtration. The resultant filtrateis then evaporated to dryness and the residual solid yellow residuecrystallized from 250 cc. of water containing a trace of ethanol afterclarification with charcoal. The resultant product, 2.5 g. of a whitesolid, p-(2,5-dihydroxyphenyl)-benzoic acid, exhibits an M.P. at 222 C.Concentration of the mother liquor to 50 cc. results in an additionalyield of 0.3 g. of the desired product exhibiting an M.P. at 218 C.

A solution of 2.16 g. of sodium hydroxide in 40 cc. of water isdeaerated with nitrogen for 10 minutes. 3.1 g. ofp-(2,5-dihyd1'oxyphenyl)-benzoic acid is added to the solution and themixture chilled for 10 minutes. To the chilled mixture, 5.1 cc. of ethylchloroformate is added portionwise over an interval of 30 minutes. Theresultant mixture is stirred for 30 minutes during which time a Whilesolid precipitates. The mixture is then acidified with 11 cc. of 3 N.hydrochloric acid, causing a guru to separate. Contact of the gum withsmall amounts of aqueous ethanol results in solidification. The solidproduct is crystallized from aqueous ethanol and then recrystallizedfrom a benzene-hexane mixture yielding 2.5 g. of a white solid,.p-(2,5-bisoathyloxyphenyl)-benzoic acid, exhibiting an M.P. at 174 to175 C.

Analysis 0 this pr0duct.Calculated as C H O C., 61.0%; H, 4.8%. Found:C, 61.2%; H, 5.0%.

2.5 g. of p-(2,5-bis-cathyloxyphenyl)-benzoic acid are refluxed with 10cc. of thionyl chloride for 2.5 hours. Excess thionyl chloride isevaporated in vacuo and the residual oil mixed with benzene. The benzeneis then evaporated and the residual oil further purified by a secondbenzene treatment. The resultant product, an oil, p-(2,5-bisoathyloxyphenyl)-benzoyl chloride, may be utilized in thesubsequent reaction without further purification.

To the above product, 0.94 g. of p-nitroaniline and 0.55 cc. of pyridinein 20 cc. of benzene are added and the mixture refluxed for 1 hour. Themixture is then cooled, extracted with water and the organic layerseparated, dried over magnesium sulfate and filtered into 15 0 cc. ofhexane. An orange gum separates which solidifies upon standing overnightand is crystallized from 215 cc. of ethanol yielding 2.5 g. of a Whitesolid, 4-( p-[2,5-bis-cathyloxyphenyl] phenylcarboxamido nitrobenzene[Formula 10], melting at 138 to 139 C.

Where desired the product of the above reaction may be deesterified, forexample, by hydrolysis in the presence of alkali, to yield,4-(p-[2',5'-dihydroxyphenyl]-phenylcarboxamido)-nitrobenzene [Formula9].

A mixture of 2.5 g. of4-(p-[2',5'bis-cavthyloxyphenyl]phenylcarboxamido)-nitrobenzene [Formula10], cc. of ethanol and 5 g. of 7% palladium/barium sulfate catalyst ishydrogenated at 30 p.s.i. of hydrogen. Theoretical uptake occurs in 1hour. The catalyst is removed by filtration and the filtrate evaporatedto dryness. Triturating the residual oil with 20 cc. of cold 1:1hydrochloric acid yields a white solid product which is crystallizedfrom 40 cc. of ethanol yielding 1.7 g. of a white amorphous solid,4-(p[2,S bis-cathyloxyphenyl]-phenylcarboxamido)-aniline hydrochloride,[the hydrochloride acid addition salt of Formula 8], which decomposes at203 C.

Where desired the product of the above reaction may be deesterified,such as for example, by hydrolysis in the presence of alkali, to yield4-(p-[2,5-dihydroxyphenyl]- phenylcarboxamido)-aniline [Formula 7].

Example 2 1.7 g. (.00344 mol) of4-(p-[2,5-bis-cathyloxyphenyl]phenylcarboxamido)-aniline hydrochloride[the hydrochloride acid addition salt of Formula 8 as prepared inExample 1], are dissolved in a warm solution of 20 cc. of glacial aceticacid and 0.27 cc. (.00344 mol) of 12.5 N. hydrochloric acid. Thesolution is cooled, diazotized at 10 C. with sodium nitrite and pouredinto a 50 cc. icewater mixture. The mixture is then added, over a 30minute interval, to a mixture of 0.59 g. (.0034 mol) of 3-methyl-l-phenyl-S-pyrazolone, 50 cc. of acetone and 10 cc. of pyridine.245 cc. of 10% sodium carbonate solution are added portionwiseconcurrently with the diazo solution to maintain a pH of 7 to 8. Theresultant orangered slurry is stirred for 1 hour, filtered and thefilter cake washed with water yielding 1.7 g. (dry weight) of 4-(4'- [p(2",5" bis-oathyloxyphenyl)-plieny'lcarboxamido]-phenylazo)-3-methyl-1-phenyl-5-pyrazolone [Formula 2].

' Example 3 1.7 g. of4-(4'-[p-(2",5"-bis-cathyloxyphenyl)-phenylcarboxamido] phenylazo)3-rnethyl-l-phenyl-S-pyrazolone [Formula 2 as prepared in Example 2],are treated in vacuo with a mixture of 2 g. of potassium hydroxide, 30cc. of ethanol and 10 cc. of water with intermittent warming on a steambath for 3 minutes. The product is precipitated with a dilutehydrochloric acid solution, the resultant slurry filtered and the filtercake washed with water. The dye is further purified by dissolving it ina methylcellosolve solution, precipitating with a 1% hydrochloric acidsolution and washing with hot water. A yield of 0.9 g. (dry weight) of4-(4'-[p-2",5-dihydroxyphenyl) phenylcarboxamido] phenylazo) 3-methyl-1-phenyl-S-pyrazolone [Formula 1], is obtained which decomposes at 258 to260 C. The spectral absorption curve of this product exhibits a A at 425my in ethanol; e=33,000.

As previously mentioned, the novel dihydroxyphenyl compounds of thisinvention, that is compounds in which the terms R and R of Formula 1 areboth hydroxlyl groups, are useful dye developers. In the followingexamples all parts are given by weight except where otherwise noted, andall operations involving light-sensitive materials are carried out inthe absence of actinic radiation. These examples are intended to beillustrative only of the photographic use of the dye developers andshould not be construed as limiting the invention in any way.

Example 4 A photosensitive element is prepared by coating agelatin-coated film base with a solution containing 3% of4-(4'-[p-(2",5-dihydroxyphenyl) phenylcarboxamido]-phenylazo)-3-methyl-l-phenyl-S-pyrazolone [Formula 1 as prepared inExample 3], in a 4% solution of cellulose acetate hydrogen phthalate ina 50:50 mixture, by volume, of acetone and tetrahydrofuran. After thiscoating has dried, a silver iodobromide emulsion is applied. Thisphotosensitive element is exposed and processed by spreading an aqueousliquid processing composition comprising:

Percent Sodium carboxymethyl cellulose 4.5 l-phenyl-B-pyrazolidone 0.2Sodium hydroxide 5.0 Potassium bromide 0.2

between said photosensitive element and an image-receiving element assaid elements are brought into superposed relationship. Theimage-receiving element comprises a cellulose acetate-coated barytapaper which has been coated with a solution comprising 4% Nylon Type F8(trade name for N-methoxymethyl polyhexamethylene adipamide) in 80%aqueous isopropanol. After an imbibition period of approximately oneminute, the imagereceiving element is separated and contains ayelloworange positive dye image of the photographed subject.

The following example illustrates the use of the dye developer in thesilver halide emulsion, instead of placing it in a layer behind thephotosensitive emulsion.

Example Percent Sodium carboxymethyl cellulose 4.51-phenyl-3-pyrazolidone 0.2 Sodium hydroxide 1.0 Potassium bromide 0.2

between said photosensitive element and an image-receiving element assaid elements are brought into superposed relationship. Theimage-receiving element comprises a cellulose acetate-coated barytapaper which has been coated with a solution comprising 4% Nylon Type F8in aqueous isopropanol. After an imbibition period of approximately oneminute, the image-receiving element is separated and contains ayellow-orange positive dye image of the photographed subject.

The dye developers of this invention are also useful in integralmultilayer photosensitive elements for use in multicolor diffusiontransfer processes. As an example of such photosensitive elements,mention may be made of the photosensitive elements disclosed and claimedin the copending U.S. application of Edwin H. Land and Howard G. Rogers,Serial No. 565,135, filed February 13, 1956, wherein at least twoselectively sensitized photosensitive strata are superposed on a singlesupport and are processed, simultaneously and without separation, with asingle common image-receiving element. A suitable arrangement of thistype comprises a support carrying a red-sensitive silver halide emulsionstratum, a greensensitive silver halide emulsion stratum and ablue-sensitive silver halide emulsion stratum, said emulsions havingassociated therewith, respectively, a cyan dye developer, a magenta dyedeveloper and a yellow dye developer. In one of the preferredembodiments of photosensitive elements of this type, the dye developersare disposed in separate alkali-permeable layers behind thephotosensitive silver halide emulsion stratum with which they areassociated.

The photosensitive elements within the scope of this invention may beused in roll film units which contain a plurality of photosensitiveframes. The photosensitive elements of this invention are especiallyuseful in composite roll film intended for use in a Polaroid Landcamera, or a similar camera structure such, for example, as the cameraforming the subject matter of U.S. Patent No. 2,435,717, issued to EdwinH. Land on February 10, 1948. In general, such composite roll filmscomprise a photosensitive roll, a roll of image-receiving material and aplurality of pods containing an aqueous alkaline processing solution.The rolls and pods are so associated with each other that, uponprocessing, the photosensitive element may be superposed on theimage-receiving element and the pods may be ruptured to spread theaqueous alkaline processing solution between the superposed elements.The nature and construction of the pods used in such units are wellknown to the art. See, for example, U.S. Patents Nos. 2,543,181 and2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain oneor more auxiliary or accelerating silver halide developing agents, suchas p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol);benzylaminophenol; hydroquinone; a substituted hydroquinone such astoluhydroquinone, phenylhydroquinone, or 4'-methylphenylhydroquinone; ora 3-pyrazolidone such as l-phenyl-3-pyrazolidone. These silver halidedeveloping agents are substantially colorless, at least in theirunoxidized form. It is possible that some of the dye developer oxidizedin exposed areas may be oxidized by an energy transfer reaction withoxidized auxiliary developing agent.

In addition, development may be effected by the presence of an oniumcompound, particularly a quaternary ammonium compound, in accordancewith the processes disclosed and claimed in the copending application ofMilton Green and Howard G. Rogers, Serial No. 50,851, filed August 22,1960, and now Patent No. 3,173,786.

The dye developers of this invention may be used also in conventionalphotographic processes, such as tray or tank development of conventionalphotosensitive films, plates or papers to obtain black and white,monochromatic or toned prints or negatives. By way of example, a

developer composition suitable for such use may comprise an aqueoussolution of approximately 1-2% of the dye developer, 1% sodiumhydroxide, 2% sodium sulfite and 0.05% potassium bromide. Afterdevelopment is completed, any unreacted dye developer is washed out ofthe photosensitive element, preferably with an alkaline Washing mediumor other medium in which the unreacted dye developer is soluble. Theexpression toned is used to designate photographic images wherein thesilver is retained With the precipitated dye, whereas monochromatic isintended to designate dye images free of silver.

It should be noted that the dye developers of this medium areself-sufiicient to provide the desired color image and do not dependupon coupling reactions to produce the desired color. They thus providea complete departure from conventional photographic color processes inwhich the color is produced by a coupling reaction between a colorformer or coupler and the oxidized developing agent, as Well as socalledauto-coupling processes in which color is obtained by a reaction of theoxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of theimage-receiving element from among suitable known opaque and transparentmaterials, it is possible to obtain either a colored positive reflectionprint or a colored positive transparency. Likewise, the inventiveconcepts herein set forth are adaptable for multicolor work by the useof special photographic materials, for example, film materials of thetype containing two or more photosensitized elements associated with anappropriate number of imagereceiving elements and adapted to be treatedwith one or more liquid processing compositions, appropriate dyedevelopers suitable to impart the desired subtractive colors beingincorporated in the photosensitized elements or in the liquid processingcompositions. Examples of such photographic materials are disclosed inUS. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made ofnylon, e.g., N-methoxymethyl-polyhexamethylene adipamide, polyvinylalcohol, and gelatin, particularly polyvinyl alcohol or gelatincontaining a dye mordant such as poly-4-vinylpyridine. Theimagereceiving element also may contain a development restrainer, e.g.,1-phenyl-5-mercaptotetrazole, as disclosed in the copending applicationof Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filedAugust 22, 1960.

The dye developers herein set forth are also useful in the formation ofcolored images in accordance with the photographic products andprocesses described and claimed in US. Patent No. 2,968,554, issued toEdwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyesfor textile fibres, such as nylon.

In the preceding portions of the specification the expression color hasbeen frequently used. This expression is intended to include the use ofa plurality of colors to obtain black.

Since certain changes may be made in the above product Without departingfrom the scope of the invention herein involved, it is intended that allmatter contained in the above description shall be interpreted asillustrative and not in a limiting sense.

I ll Z-N-O I B n is the residue of a monoazo dye molecule R Zita] andwherein Z represents the azo dye molecule other than the amino group orgroups; R is a member of the group consisting of hydrogen and loweralkyl radicals; R and R each are selected from the group consisting ofhydroxy and carbethoxy; and n is a positive integer from 1 to 2.

2. 4-(4'-[p-(2",5-dihydroxyphenyl) phenylcarboxamido] phenylazo -3-methyll-phenyl-S -pyrazolone.

3. 4-(4-[p-(2,5-bis cathyloxyphenyl) phenylcarboxamido] -phenylazo)-3-methyl-1-phenyl-5-pyrazolone.

4. 2-(4-[p-(2,5-dihydroxyphenyl) phenylcarboxamido] -phenylazo)-4-methoxy-1-naphthol.

5. 2-(4'-[p-(2,5-bis cathyloxyphenyl) phenylcarboxamido] -phenylazo)-4-methoxy-l-naphthol.

6. 3-carbethoxy-4-(4-[m (2",5" dihydroxyphenyl)- phenyloarboxamido]-phenylazo) -1-phenyl-5-pyrazolone.

7. 1-(4'-[m-(2,5 di-hydroxyphenyl) benzamido]-phenyl)-3,N,N-dimethylcarboxamido-4-(2',4,6-trimethylphenylazo)-5-pyrazolor1e.

wherein References Cited by the Examiner UNITED STATES PATENTS 2,715,1208/1955 Ruegg et al 260-162 2,816,103 12/1957 Schmid 260-162 2,983,606 5/1961 Rogers 96-29 2,997,390 8/1961 Land 96-29 3,009,958 11/1961 Green etal. 96-29 3,019,107 1/1962 Blout et al. 96-66 3,036,128 5/1962 Moffett260-559 3,047,627 7/1962 Greenlee 260-559 3,134,764 5/1964 Blout et al.260-162 3,135,734 6/1964 Green et al 260-162 FOREIGN PATENTS 554,2127/1957 Belgium. 1,047,620 12/ 1958 Germany.

OTHER REFERENCES Lubs, The Chemistry of Synthetic Dyes and Pigments,Reinhold, New York, 1955, page 670.

Venkatoraraman, The Chemistry of Synthetic Dyes," vol. 1, AcademicPress, Inc., New York, 1952, pages 358 and 359.

CHARLES B. PARKER, Primary Examiner. L. ZITVER, Examiner.

REYNOLD I. FINNEGAN, D. M. PAPUGA,

Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,262,924 July 26, 1966 Milton Green It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column 3, lines 25 to 39, the lower left-hand portion of the formulashould appear as shown below instead of as in the patent:

O- C-OC H column 4, lines 40 and 41, for "Z-(p-aminophenylazo) 4-phenylazo-S-pyrazolone, etc." read 2(p-aminophenylazo)4methoxylnaphthol; l-(p-aminophenyl)3-N,N-dimethylcarboxamido-4phenylaz0-5pyrazolone, etc, column 7, lines10 and 11, for "4(4 -[p2' ,5-dihydroxy" read 4- 4 2, 5 dihydroxycolumn8, line 65, for "by" read in column 10, line 23, for "carbethoxy" readcathyloxy lines 24 and 25, for "-phenylcarboxamido1" read -phenylcarboxamido] Signed and sealed this 5th day of September 1967.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. A MONOAZO DYE OF THE FORMULA: